Construction of Cyclodextrin-based Impedance Sensor for Recognition of L-Cysteine †

doi:10.7503/cjcu20190584

Abstract

Abstract:

By means of quantum chemical calculation, the supramolecular interaction between the γ-cyclodextrin(γ-CD) as the host and the L-cysteine(L-Cys) oxidation product as the guest was simulated from the molecular level. The weak interaction energy(E_L) between γ-CD and L-Cys oxidation product reaches -12.6 eV, which is 3.7 times different from the interaction between γ-CD and D-Cys oxidation product(E_D=-2.7 eV). Their intramolecular hydrogen bonds exist nearly doubled difference. Based on the theoretical simulation, an γ-CD modified impedance sensor was constructed for sensitive and specific impedance identification of L-Cys. Using potassium ferricyanide(Ⅱ/Ⅲ) as the redox probe, the electrochemical transfer impedance(R_et) linearly changed with the concentration of L-Cys between 0.1 μmol/L and 1.0 μmol/L(stage one), and from 1.0 μmol/L and 6.0 μmol/L(stage two), with the detection limit of 74 nmol/L(S/N=3). Compared with the unmodified glassy carbon electrode, the sensitivity for the impedance response of L-Cys has been increased about 19 times. Meanwhile, the selectivity to the thiol-containing structural analog is significantly improved by this cyclodextrin-based sensor, successfully applied for the detection in human serum and drug capsules with average recoveries between 88.9% and 108%. This study establishes a novel, low-cost, simple, quantitative identification method for chiral compounds with weak electrical property, providing a potential strategy for electrochemical analysis of chiral targets.

Key words: L-Cysteine, Impedance recognition, Electrochemical sensor, Cyclodextrin, Electrodeposition sensing

CLC Number:

O657

TrendMD:

FU Kefei, LIAN Huiting, WEI Xiaofeng, SUN Xiangying, LIU Bin. Construction of Cyclodextrin-based Impedance Sensor for Recognition of L-Cysteine ^†[J]. Chem. J. Chinese Universities, 2020, 41(4): 706.

Figures/Tables 13

Scheme 1 Schematic description of the preparation and sensing of γ-CD-based electrochemical sensor

Fig.1 CV(A) and DPV(B) responses of L-Cys on GCE

Scheme 2 Oxidation mechanism of L-Cys

Structural analogue	L-Cys	D-Cys	Hcy	L-Pen	D-Pen
ΔR_L_-Cys/ΔR_other	1	1.179	2.120	1.511	1.513

Fig.3 Electro-oxidation(A, C) and desorption(B, D) on bare GCE(A, B) and γ-CD-based sensor(C, D)

Fig.4 Molecular occupied orbitals 152(A), 369(B), 387(C), 388(D), 389(E), 391(F) for γ-CD-L-Cys and 360(G), 367(H), 390(I), 394(J), 396(K), 397(L) for γ-CD-D-Cys

Fig.5 Effect of different types of CDs(A), concentrations of γ-CD(B), pH changing(C), temperature changing(D) and assembling time(E) on the γ-CD self-assembly on GCE

Fig.6 SEM image(A) and FTIR spectra(B) of self-assembled γ-CD, EIS(C) and CVs(D) spectra of γ-CD-based sensor and bare GCE

Fig.7 Effect of different means(A) and concentrations of [Fe(CN)6]3-/4-(B) on the γ-CD-based sensor (A) a. DPV, 0—1.0 V; b. stewing 65 s; c. CV, 0—1.0 V.

Fig.8 EIS(A) and calibration curve(B) for the detection of L-Cys with 0.1—6.0 μmol/L on γ-CD-based sensor and the comparison(C) of calibration curves for L-Cys on γ-CD-based sensor or bare GCE

Fig.9 Impedance responses(A) of various structural analogues on γ-CD-based sensor and selectivity analysis(B) for detection of L-Cys on γ-CD-based sensor and bare GCE

Structural analogue	L-Cys	D-Cys	Hcy	L-Pen	D-Pen
ΔR_L-Cys/ΔR_other	1.000	2.301	2.578	2.724	2.861

Sample	Added/(μmol·L^-1)	Found/(μmol·L^-1)	Recovery(%)	RSD(%)(n=3)
Blood serum	0	0.218		1.0
	0.300	0.542	108.0	0.9
	0.500	0.691	94.8	2.0
	0.700	0.910	98.9	1.5
Capsule	0	0.045		0.9
	0.300	0.317	90.6	0.6
	0.500	0.531	97.2	0.7
	0.900	0.840	88.9	0.4

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